3-substituted derivatives of 2, 3-dihydrothianaphthene-1-dioxide



Patented Sept. 9, 1952 UNITEDSTATES EN bF mE 3-SUBS TITUTED-DERIVATIVES OF 2,3-DIHY- -DROTHIANAPHTHENE-1-DIQXIDE Wilbur n. McKellin and Frederick G. Bor dwell,' Evanston, 111., assignors to The Texas Company, New YorlnN. Y., a corporation of Delaware No Drawing. Application September 26, 1949, Serial N 0. 117,938

wherein X is a secondary amino group. The novel compounds of this invention include addition products of thianaphthene-l-dioxide with cyclic secondary amines, such as morpholine and piperidine. Addition products of thianaphthenel-dioxide and aliphatic secondary amine, such as diethylamine, are the more common members of the novel addition products of this invention.

The novel compounds of this invention are crystalline solids which are useful as pesticides, pharmaceuticals and as chemical intermediates in the preparation of pesticides, pharmaceuticals and lub oil additives.

The addition products of thianaphthene-l-dioxide and secondary amines are very simply prepared. The two reactants, namely, thianaphthene-l-dioxide and secondary amine, are heated under reflux for a period of time; thereafter the adduct is isolated from the reaction mixture. The following examples illustrate the simple manner in which the novel compounds of this invention can be prepared. However, it will be understood that the novel compounds of this invention are in no way restricted to any one mode of preparation.

Example I 0.1 g. of thianaphthene-l-dioxide, 1.0 g, of piperidine and 15 cc. of 95 per cent alcohol were refluxed for 15 minutes. Thereafter, the alcohol was removed from the reaction mixture by a current of air. A quantitive yield of 3-piperidino- 2 3 dihydrothianaphthene -1 dioxide was obtained; the crude product had a melting point of r 103 to 110 C. On recrystallization from dilute alcohol a pure product was obtained having a melting point of 109 to 110 C. Analysis of this purified sample indicated that it contained 62.11 per cent carbon and 6.83 per cent hydrogen as compared with calculated theoretical values of 62.12 per cent and 6.82 per cent fortheelements in the order named. 3-piperidino-2,3-dihydrothianaphthene 1 dioxide has the following structural formula:

/H H2 H2 Q Hg H2 H1 Example H 0.5 g. of thianaphthene-l-dioxide, 0.5 g. of morpholine and 20 cc. of water were refluxed 1 hours. Upon cooling there was obtained a quantitive yield of 3-morpholino-2,3-dihydrothianaphthene 1 dioxide melting at 176 to 179 C. On recrystallization from alcohol a pure product was obtained melting at 177.5 to 178.5 C. Analysis of this product indicated that it'contained 5.76 per cent nitrogen as compared with a calculated theoretical value of 5.53 per cent. 3 morpholino 2,3 dihydrothianaphthene 1- dioxide has the following structural formula:

Example III ""he foregoing examples illustrate a method of preparing the novel compounds of this invention. As indicated previously, other prepar ative procedures may be employed to prepare the novel compounds of this invention. Moreover, secondary amines other than those employed in the foregoing examples react with 3 thianaphthene-l-dioxide to yield addition products which are members of the novel class of compounds of this invention.

Obviously, many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore, only such limitations should be imposed as are indicated in the appended claims.

We claim:

1. 2,3-dihydrothianaphthene 1-dioxide com-- pounds having the general formula:

wherein X is a secondary amino group selected from the group consisting of dialkyl amino, piperidin and morpholino radicals.

2. 3 piperidino 2,3 dihydrothianaphthenel-dioxide.

4 3. 3 morpholino 2,3 dihydrothianaphthene-l-dioxide.

4. 3 diethylamino 2,3 dihydrothianaphthene-l-dioxide. 5 WILBUR I-I. McKELLIN.

FREDERICK G. BORDWELL.

REFERENCES CITED The following references are of record in the 10 file of this patent:

UNITED STATES PATENTS OTHER. REFERENCES Bar-dwell et al., Jour. Amer. Chem. 500., vol. 20 70 (1948), pages 1558-1560. 

1. 2,3-DIHYDROTHIANAPHTHENE-1-DIOXIDE COMPOUNDS HAVING THE GENERAL FORMULA: 